To increase flexible property of epoxy resin and decrease curing temperature of silicone modified epoxy resin, the epoxy/polysiloxane hybrid materials are prepared by crosslinking hybrid of epoxy endgroup polysiloxane and epoxy resin via UV curing technology under a cationic photoinitiator. The structures and properties of epoxy/polysiloxane hybrid films are investigated by 13C NMR, 29Si NMR, SEM, FTIR, and UV-vis analyzer, respectively. It is found that epoxy/polysiloxane films are obtained by in-situ crosslinking reaction under UV curing process without the phase separation. The epoxy/polysiloxane hybrid films have excellent transparence, thermal resistance, UV blocking and high adhesive properties, which can be applied to various optical fields such as the LED encapsulation materials and electronic encapsulation materials.